2-Amino-5-arylazoarylazothiazole compounds

ABSTRACT

Acid azo dyes containing thiazole coupling components, of the general formula ##STR1## where D is the radical of a diazo component, 
     R is hydrogen, acetyl, benzoyl or an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, 
     R 1  and R 2  independently of one another are optionally substituted alkyl, cycloalkyl, aralkyl or aryl, 
     R 1  may also be hydrogen and 
     R 1  and R 2  together with the nitrogen may be a heterocyclic radical, and 
     the radicals D, R, R 1  and/or R 2  may in total contain from 1 to 4 --SO 3  H groups. 
     The deeply colored novel compounds are particularly suitable for dyeing polyamides, and the dyeings obtained have very good lightfastness and wetfastness.

The present invention provides novel compounds of the general formula I##STR2## where D is the radical of a diazo component,

R is hydrogen, C-acyl or an aliphatic, cycloaliphatic, aromatic orheterocyclic radical,

R¹ and R² independently of one another are optionally substituted alkyl,cycloalkyl, aralkyl or aryl, and

R¹ may also be hydrogen, or

R¹ and R² together with the nitrogen form a heterocyclic radical, andthe molecule contains from 1 to 4 --SO₃ H groups in the radicals D, R,R¹ and/or R².

Radicals D may in particular be derived from compounds of the aniline,aminonaphthalene, aminoanthraquinone or aminophthalimide series or fromheterocyclic compounds such as thiazoles, benzthiazoles,benzisothiazoles, indazoles or pyrazoles.

Examples of suitable substituents for radicals D of the aromatic series(i.e. aniline, aminonaphthalene, aminoanthraquinone and aminophthalimideseries) are fluorine, chlorine, bromine, trifluoromethyl, C₁ -C₄ -alkyl,C₁ -C₄ alkoxy, hydroxyl, amino, C₁ -C₄ -alkanoylamino, benzoylamino, C₁-C₄ -monoalkylamino and -dialkylamino, carboxyl, C₁ -C₄ -alkoxycarbonyl,nitro, cyano, carbamoyl, sulfamoyl, C₁ -C₄ -alkylsulfonyl andphenylsulfonyl.

Examples of suitable substituents for heterocyclic radicals D are nitro,cyano, chlorine, bromine, carboxyl, hydroxyl, C₁ -C₄ -alkoxycarbonyl andcarbamoyl.

Preferred diazo components correspond to the general formula ##STR3##where X¹ is hydrogen, fluorine, chlorine, bromine, nitro, cyano,methylsulfonyl, ethylsulfonyl, hydroxyl, carboxyl, C₁ -C₄-alkoxycarbonyl, carbamoyl, methyl, ethyl, methoxy, ethoxy, sulfamoyl orhydroxysulfonyl,

X² is hydrogen, chlorine, bromine, nitro, cyano or hydroxysulfonyl,

X³ is hydrogen, chlorine, bromine or hydroxysulfonyl,

X⁴ is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy, C₁ -C₄-alkanoylamino, hydroxyl or hydroxysulfonyl,

X⁵ is hydrogen, methyl, ethyl, methoxy or ethoxy, and the dotted linesrepresent optional aromatic rings fused to the benzene rings shown.

Specific examples of diazo components DNH₂ are aniline, o-, m- andp-chloroaniline, o-, m- and p-bromoaniline, o-, m- and p-nitroaniline,o-, m- and p-toluidine, o-, m- and p-anisidine, o-, m- andp-phenetidine, o-, m- and p-ethylaniline, 2-chloro-4-aminotoluene,4-chloro-2-aminotoluene, 6-chloro-2-aminotoluene,5-amino-1,4-dimethylbenzene, 2-chloro-5-methoxyaniline,2-chloro-5-ethoxyaniline, 2,5-dichloroaniline, 3,4-dichloroaniline,2,4-dichloroaniline, 2,6-dichloroaniline, 1-aminobenzene-2-sulfonicacid, 1-aminobenzene-3-sulfonic acid, 1-aminobenzene-4-sulfonic acid,2,5-dichloro-1-aminobenzene-4-sulfonic acid,2,6-dibromo-1-aminobenzene-4-sulfonic acid,1-aminobenzene-2,4-disulfonic acid, 1-aminobenzene-2,5-disulfonic acid,2-chloro-1-aminobenzene-4-sulfonic acid,2-chloro-1-aminobenzene-5-sulfonic acid,4-chloro-1-aminobenzene-5-sulfonic acid,4-nitro-1-aminobenzene-2-sulfonic acid,2-nitro-1-aminobenzene-4-sulfonic acid, 1-aminobenzene-2-carboxylicacid, 5-sulfo-2-amino-benzoic acid and ##STR4##

Examples of radicals R are acetyl, benzoyl, C₁ -C₄ -alkyl which isunsubstituted or substituted by chlorine, bromine, cyano, hydroxyl, C₁-C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylmercapto, phenoxy,sulfophenoxy, phenylmercapto, amino, N-mono- or N,N-di-C₁ -C₄-alkylamino, phenylamino, sulfophenylamino, C₁ -C₄ -alkanoylamino orsulfoethylamino, vinyl, cyclohexyl, and phenyl, thienyl and thiazolylwhich are unsubstituted or substituted by fluorine, chlorine, bromine,hydroxyl, C₁ -C₄ -alkoxy, β-C₁ -C₄ -alkanoyloxyethoxy, β-cyanoethoxy,β-carboxylethoxy, β-C₁ -C₄ -alkoxycarbonylethoxy, phenoxy, sulfophenoxy,C₁ -C₄ -alkylmercapto, phenylmercapto, amino, β-C₁ -C₄ -alkanoylamino,benzoylamino, C₁ -C₄ -monoalkylamino or -dialkylamino, phenylamino,sulfophenylamino, C₁ -C₄ -alkylsulfonylamino, phenylsulfonylamino andhydroxysulfonyl.

Specific examples of radicals R are: CH₃, C₂ H₅, CH₂ Cl, CH₂ CN, CH₂ OH,CH₂ --CH₂ Cl, CH₂ --CH₂ OH, CH₂ --CH₂ CN, CH₂ --COOCH₃, CH₂ COOC₂ H₅,CH₂ --COOH, CH₂ --NHC₂ H₄ SO₃ H, --CH₂ OCH₃, --CH₂ OCH₃, --CH₂ OC₂ H₅,CH₂ SCH₃, CH₂ N(CH₃)₂, C₆ H₅ OCH₂, HO₃ SC₆ H₄ OCH₂, C₆ H₅, ClC₆ H₄, BrC₆H₄, FC₆ H₄, Cl₂ C₆ H₃, CH₃ C₆ H₄, (CH₃)₂ C₆ H₃, CH₃ OC₆ H₄, C₂ H₅ OC₆H₄, NCC₂ H₄ OC₆ H₄, CH₃ OOC.C₂ H₄ OC₆ H₄, HOOC--C₂ H.sub. 4 OC₆ H₄, H₂NCOC₂ H₄ OC₆ H₄, CH₃ COOC₂ H₄ OC₆ H₄, HOC₂ H₄ OC₆ H₄, HOC₆ H₄, C₆ H₅ OC₆H₄, HO₃ SC₆ H₄ --OC₆ H₄, CH₃ SC₆ H₄, C₆ H₅ SC₆ H₄, NC--C₂ H₄ SC₆ H₄, CH₃CONHC₆ H₄, C₂ H₅ CONHC₆ H₄, H₂ N--C₆ H₄, HOC₂ H₄ NHC₆ H₄, (C₂ H₅)₂ NC₆H₄, CH₃ SO₂ NHC₆ H₄, C₆ H₅ SO₂ NHC₆ H₄, C₆ H₅ NHC₆ H₄, CH₃ CONHC₆ H₃ SO₃H, CH₃ OC₆ H₃ SO₃ H, ##STR5##

Examples of radicals R¹ and R² are C₁ -C₈ -alkyl radicals which may beinterrupted by oxygen and substituted by hydroxyl, carboxyl, cyano,chlorine, bromine, phenyl, C₁ -C₈ -alkoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄-alkoxycarbonyl, C₁ -C₄ -alkanoylamino, acetyl, C₁ -C₄-alkylaminocarbonyloxy, arylamino-carbonyloxy, C₁ -C₄ -alkoxycarbonyloxyor phenoxycarbonyloxy, allyl, methallyl, propargyl, cyclohexyl,phenyl-C₁ -C₅ -alkyl or phenyl or naphthyl which are unsubstituted orsubstituted by fluorine, chlorine, bromine, C₁ -C₄ -alkoxycarbonyl,carboxyl, nitro or C₁ -C₄ -alkanoylamino. All aromatic radicals, whichpreferably contain phenyl or naphthyl groups, can, in the above list, besubstituted by hydroxysulfonyl; furthermore, the aliphatic radicals maycarry one or more sulfonic acid groups.

Specific examples of radicals R¹ and R², in addition to those alreadymentioned, are hydrogen, methyl, ethyl, propyl, butyl, β-hydroxyethyl,β-methoxyethyl, γ-methoxypropyl, β-cyanoethyl, β-carbomethoxyethyl,β-carboethoxyethyl, β-acetoxyethyl, β-ethoxycarbonylethyl,γ-acetylaminopropyl, phenoxycarbonyloxyethyl,phenylaminocarbonyloxyethyl, butylaminocarbonyloxyethyl, benzyl,β-phenylethyl, phenyl, sulfophenyl, disulfophenyl, acetylaminophenyl,carboxyphenyl, cyanophenyl, chlorophenyl and sulfoethyl, as well as##STR6##

R¹ and R² together with the nitrogen may for example the pyrrolidino,piperidino, morpholino, piperazino, α-methylpiperazino,hexamethyleneimino or thiomorpholino-S-dioxide.

A compound of the general formula I may be prepared by reacting adiazonium compound of an amine of the general formula III

    DNH.sub.2                                                  III

with a coupling component of the general formula IV ##STR7##

Some sulfo-group-containing dyes of the general formula I can also beprepared by sulfonating corresponding dyes which are free from sulfogroups, or contain fewer sulfo groups.

Compounds of the general formula IV containing one or more sulfo groupsare novel; they may contain the SO₃ H group or groups in one or both ofthe radicals R and R¹, whilst R² is hydrogen. These coupling componentsmay be prepared by reacting a compound of the general formula ##STR8##with a primary amine of the general formula

    H.sub.2 N--R.sup.1

to give a compound of the general formula ##STR9## Depending on thestarting components, the SO₃ H group or groups may be present in one orboth of the radicals R and R¹, the presence of SO₃ H in R¹ beingpreferred.

The methods of preparation of the dyes are known in principle. Detailsmay be found in the Examples, where parts and percentages are by weightunless stated otherwise.

The preferred use of the compounds of the general formula I is fordyeing nitrogen-containing fibers, eg. wool, silk and especially nylons.Some of the compounds may also be used for dyeing leather.

The dyeings are distinguished by good lightfastness and wetfastness,such as fastness to water, perspiration, brine and fulling treatments.The high tinctorial strength of the compounds of the general formula Ialso deserves special mention.

Compounds of particular industrial importance are those of the generalformula I a ##STR10## where D¹ is phenyl or naphthyl substituted byarylazo,

B is C₁ -C₄ -alkyl, β-carboxymethyl or phenyl which is unsubstituted orsubstituted by chlorine, bromine, methyl, ethyl, C₁ -C₄ -alkoxy,β-cyanoethoxy, β-carboxyethoxy, phenoxy, sulfophenoxy, C₁ -C₄-alkanoylamino, phenylamino, sulfophenylamino or hydroxysulfonyl, and

B¹ and B² independently of one another are C₁ -C₈ -alkyl, C₂ -C₈ -alkylwhich is substituted by hydroxyl, carboxyl, hydroxysulfonyl, cyano,phenyl, C₁ -C₈ -alkoxy, phenoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄-alkoxycarbonyl, C₁ -C₄ -alkanoylamino or C₁ -C₄ -alkoxycarbonyloxy,allyl, phenyl-C₁ -C₅ -alkyl or phenyl or naphthyl which areunsubstituted or substituted by chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, cyano, carbamoyl or hydroxysulfonyl.

EXAMPLE 1 A. Preparation of 4-phenyl-2-(3-sulfophenylamino)-thiazole

132 parts of phenacyl thiocyanate, 38 parts of zinc chloride and 129parts of 1-aminobenzene-3-sulfonic acid are together stirred with 750parts of water for 20 hours at the boil. After the mixture has cooled,the product is filtered off and dried.

Yield: 224 parts (about 90% of theory).

4-Phenyl-2-(4-sulfophenylamino)-thiazole can be prepared similarly, inabout 80% yield.

B. Preparation of the Dye

17.3 Parts of 1-aminobenzene-3-sulfonic acid are dissolved in 100 partsof water and sufficient 5 N sodium hydroxide solution to give a neutralmixture, and after adding an aqueous solution of 6.9 parts of sodiumnitrite, the batch is added dropwise to a mixture of 100 parts of water,100 parts of ice and 60 parts of 5 N hydrochloric acid at 0°-5° C.,whilst stirring. After 1 hour, the excess nitrite is destroyed withamidosulfonic acid, and a solution of 22.3 parts of a mixture of1-naphthylamine-6-and -7-sulfonic acid in 200 parts of water and 8 partsof 50% strength sodium hydroxide solution is then added in the course of30 minutes. Thereafter, the pH is raised to 2.5 by means of dilutesodium hydroxide solution. After completion of coupling, the monoazo dyeis dissolved by means of sodium hydroxide solution, to give a final pHof 6-7, and after adding an aqueous solution of 7.0 parts of sodiumnitrite the batch is added to a mixture of 150 parts of ice, 100 partsof water and 80 parts of 5 N hydrochloric acid, whilst stirring. Thediazotization is complete after about 4 hours at from 10° to 15° C. Theexcess nitrite is destroyed with amidosulfonic acid and a solution of 35parts of 4-phenyl-2-(3-sulfophenylamino)-thiazole in 400 parts of waterand 8 parts of 50% strength sodium hydroxide solution is added dropwiseto the suspension of the diazonium salt. The batch is then brought to apH of 10 with dilute sodium hydroxide solution. After completion ofcoupling, the disazo dye is salted out at a pH of 7-8 by means of 200parts of potassium chloride, and is filtered off and dried under reducedpressure at 60° C.

A dark powder is obtained, which corresponds to the formula ##STR11##and gives reddish dark blue dyeings, having good light-fastness andwetfastness, on nylon 6.

The dyes characterized by their substituents in the Table which followscan be prepared similarly to Example 1 and give dyeings in blue hues,having similar properties to the above.

    __________________________________________________________________________     ##STR12##                                                                    Ex-                                                                           ample                                                                             D.sup.1                B          B.sup.1    B.sup.2                      __________________________________________________________________________         ##STR13##             C.sub.6 H.sub.5                                                                           ##STR14## H                            3                                                                                  ##STR15##             "          "          H                            4                                                                                  ##STR16##             "          "          H                            5                                                                                  ##STR17##             "          "          H                            6                                                                                  ##STR18##             "          "          H                            7                                                                                  ##STR19##             "          "          H                            8                                                                                  ##STR20##             "          "          H                            9                                                                                  ##STR21##             "                                                                                         ##STR22## H                            10  "                                                                                                     ##STR23## "          H                            11  "                                                                                                     ##STR24## "          H                            12                                                                                 ##STR25##                                                                                            ##STR26## "          H                            13                                                                                 ##STR27##                                                                                            ##STR28##                                                                                ##STR29## H                            14                                                                                 ##STR30##             C.sub.6 H.sub.5                                                                          "          H                            15                                                                                 ##STR31##             "          "          H                            16                                                                                 ##STR32##                                                                                            ##STR33## "          H                            17                                                                                 ##STR34##             "          "          H                            18                                                                                 ##STR35##             "          "          H                            19                                                                                 ##STR36##             "          "          H                            __________________________________________________________________________

EXAMPLE 20

40.7 parts of the monoazo compound prepared by diazotizing1-aminobenzene-3-sulfonic acid and coupling with1-aminonaphthalene-6/7-sulfonic acid are added to a solution of 8.0parts of sodium hydroxide in 900 parts of water at 50° C., and themixture is stirred until all has dissolved. It is then cooled to 0° C.and a solution of 7.0 parts of sodium nitrite in 30 parts of water isadded, followed dropwise by 25.4 parts of concentrated hydrochloric acidin 60 parts of water. The mixture is stirred for 4 hours at 0°-5° C.,the excess nitrous acid is removed with amidosulfonic acid and asolution of 30 parts of4-(4'-acetylaminophenyl)-2-(N-diallylamino)-thiazole in 50 parts ofdimethylformamide and 25 parts of water is then run into the diazoniumsalt suspension.

The pH is then raised to 4 with aqueous sodium acetate solution. Aftercompletion of coupling, the disazo dye is salted out with potassiumchloride at 40° C., filtered off and dried under reduced pressure at 60°C. The dye has the formula ##STR37## and dyes nylon in lightfast andwetfast navy hues.

The dyes characterized by their substituents in the Table which followscan be prepared similarly to Example 20 and also give dyeings in bluehues, having similar properties to the above.

    __________________________________________________________________________     ##STR38##                                                                    Ex-                                                                           ample                                                                             D.sup.1                   B             B.sup.1    B.sup.2                __________________________________________________________________________    21                                                                                 ##STR39##                                                                                               ##STR40##    CH.sub.2 CHCH.sub.2                                                                      CH.sub.2 CHCH.sub.2                                                           5                      22                                                                                 ##STR41##                "             "          "                      23                                                                                 ##STR42##                C.sub.6 H.sub.5                                                                             C.sub.2 H.sub.5                                                                          C.sub.6 H.sub.5        24                                                                                 ##STR43##                "             CH.sub.2 CHCH.sub.2                                                                      CH.sub.2 CHCH.sub.2                                                           .                      25  "                         "             C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5        26  "                                                                                                        ##STR44##    "          "                      27  "                                                                                                        ##STR45##    "          "                      28  "                                                                                                        ##STR46##    "          "                      29                                                                                 ##STR47##                                                                                               ##STR48##    CH.sub.2 CHCH.sub.2                                                                      CH.sub.2 CHCH.sub.2    30  "                                                                                                        ##STR49##    C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5        31                                                                                 ##STR50##                C.sub.6 H.sub.5                                                                             "          "                      32                                                                                 ##STR51##                                                                                               ##STR52##    "          "                      33                                                                                 ##STR53##                                                                                               ##STR54##    "          "                      34  "                         C.sub.6 H.sub.5                                                                              ##STR55## H                      35                                                                                 ##STR56##                "             "          H                      36                                                                                 ##STR57##                "                                                                                            ##STR58## H                      37                                                                                 ##STR59##                "                                                                                            ##STR60## H                      38                                                                                 ##STR61##                "             "          H                      39                                                                                 ##STR62##                "             "          H                      __________________________________________________________________________

EXAMPLE 40 A. Preparation of 4-methyl-2-(4-sulfophenylamino)-thiazole

173 parts of 1-aminobenzene-4-sulfonic acid in 1,000 parts of 50%strength alcohol are stirred with 115 parts of thiocyanato-acetone for 5hours at the boil. The reaction mixture is then cooled to roomtemperature and the product is filtered off and dried under reducedpressure at 60° C.

Yield: 255 parts (about 94% of theory).

4-Methyl-2-(3-sulfophenylamino)-thiazole can be prepared analogously, inabout 93% yield.

B. Preparation of the dye

40.7 Parts of the monoazo dye obtained from 1-aminobenzene-4-sulfonicacid and 1-aminonaphthalene-6-sulfonic acid are diazotized as describedin Example 1. A solution of 27.0 parts of4-methyl-2-(3-sulfophenylamino)-thiazole in 200 parts of water and 8parts of 50% strength sodium hydroxide solution is then added to thediazo suspension. The reaction mixture is then brought to a pH of about4 with aqueous sodium acetate solution. After completion of coupling,the disazo dye is salted out with potassium chloride, filtered off anddried under reduced pressure at 60° C. The dye, which has the formula##STR63## dyes nylon in reddish blue hues having good lightfastness andwetfastness.

The dyes characterized in the Table which follows can be preparedsimilarly to Example 40 and give blue dyeings having similar propertiesto the above.

    __________________________________________________________________________     ##STR64##                                                                    Ex-                                                                           ample                                                                             D.sup.1           B  B.sup.1  B.sup.2                                     __________________________________________________________________________    41                                                                                 ##STR65##        CH.sub.3                                                                          ##STR66##                                                                             H                                           42                                                                                 ##STR67##        "  "        H                                           43                                                                                 ##STR68##        "  "        H                                           44                                                                                 ##STR69##        "                                                                                 ##STR70##                                                                             H                                           45                                                                                 ##STR71##        CH.sub.3                                                                          ##STR72##                                                                             H                                           46                                                                                 ##STR73##        "  "        H                                           __________________________________________________________________________

EXAMPLE 47

12.8 Parts of o-chloroaniline are dissolved in 50 parts of water and 50parts of 5 N hydrochloric acid and after adding 100 parts of ice thediazotization is carried out with a solution of 6.9 parts of sodiumnitrite at 0°-5° C., whilst stirring. After about 10 minutes, a slightexcess of nitrous acid is destroyed with a small amount of amidosulfonicacid, and the diazonium salt solution is then added, in the course of 15minutes, to a solution of 22.3 parts of 1-naphthylamine-6-sulfonic acidin 140 parts of water and 3.2 parts of sodium carbonate. The pH of themixture is then raised to 4.0 with sodium carbonate. After completion ofcoupling, the pH is brought to 12 with sodium hydroxide solution andafter adding 40 parts of sodium chloride the intermediate formed isfiltered off. The filter cake is stirred into 200 parts of water, asolution of 7.5 parts of sodium nitrite is added, and the batch is thenstirred into a mixture of 200 parts of ice and 30 parts of 32% strengthhydrochloric acid. After about 4 hours at 10°-15° C., the excess nitrousacid is removed and a solution of 35 parts of4-phenyl-2-(3-sulfophenylamino)-thiazole in 400 parts of water and 8parts of 50% strength sodium hydroxide solution is added.

The pH is then raised to 9 with sodium hydroxide solution. Aftercompletion of coupling, the pH of the batch is returned to 7 with dilutehydrochloric acid.

300 Parts of potassium chloride are then added, the mixture is heated to60° C., and the product is filtered off and dried at 60° C. underreduced pressure. A dark powder of the formula ##STR74## is obtained,which dyes nylon and other polyamide fibers in navy hues having goodwashfastness and lightfastness.

The dyes characterized in the Table which follows can be preparedsimilarly to Example 47 and give blue dyeings having similar propertiesto the above.

    __________________________________________________________________________     ##STR75##                                                                    Ex-                                                                           ample                                                                              D       B          B.sup.1  B.sup.2                                      __________________________________________________________________________    48                                                                                  ##STR76##                                                                            C.sub.6 H.sub.5                                                                           ##STR77##                                                                             H                                            49                                                                                  ##STR78##                                                                            "          "        H                                            50                                                                                  ##STR79##                                                                            "                                                                                         ##STR80##                                                                             H                                            51                                                                                  ##STR81##                                                                            "          "        H                                            52                                                                                  ##STR82##                                                                             ##STR83## "        H                                            53                                                                                  ##STR84##                                                                            C.sub.6 H.sub.5                                                                          "        H                                            54                                                                                  ##STR85##                                                                            "          "        H                                            55                                                                                  ##STR86##                                                                            "          "        H                                            56                                                                                  ##STR87##                                                                            C.sub.6 H.sub.5                                                                           ##STR88##                                                                             H                                            57                                                                                  ##STR89##                                                                            "          "        H                                            58                                                                                  ##STR90##                                                                             ##STR91## "        H                                            59                                                                                  ##STR92##                                                                            "          "        H                                            60                                                                                  ##STR93##                                                                            "          "        H                                            61                                                                                  ##STR94##                                                                            "                                                                                         ##STR95##                                                                             H                                            62   "                                                                                      ##STR96## "        H                                            __________________________________________________________________________

EXAMPLE 63

24.2 Parts of 1-amino-2,5-dichlorobenzene-4-sulfonic acid are diazotizedas described in Example 1. A solution of 35 parts of4-phenyl-2-(3-sulfophenylamino)-thiazole in 400 parts of water and 8parts of 50% strength sodium hydroxide solution is added to thenitrite-free suspension of the diazonium salt, whilst stirring. Thebatch is then brought to a pH of 7-8 with dilute sodium hydroxidesolution. After completion of coupling, the monoazo dye is salted outwith 100 parts of potassium chloride, filtered off and dried underreduced pressure at 60° C. The dye, which has the formula ##STR97## dyesnylon 6 in bluish red hues having good lightfastness and wetfastness.

The dyes summarized in the Table which follows can be prepared similarlyto Example 63 and give dyeings having similar properties.

    __________________________________________________________________________     ##STR98##                                                                    Ex-                                                                           ample                                                                             D               B       B.sup.1  B.sup.2                                                                         Hue                                    __________________________________________________________________________    64                                                                                 ##STR99##      C.sub.6 H.sub.5                                                                        ##STR100##                                                                            H bluish red                             65  "                                                                                              ##STR101##                                                                           "        H "                                      66                                                                                 ##STR102##     "       "        H "                                      67                                                                                 ##STR103##     "       "        H orange                                 68                                                                                 ##STR104##     "       "        H "                                      69                                                                                 ##STR105##                                                                                    ##STR106##                                                                            ##STR107##                                                                            H brown                                  70                                                                                 ##STR108##     C.sub.6 H.sub.5                                                                       "        H violet                                 71                                                                                 ##STR109##     C.sub.6 H.sub.5                                                                        ##STR110##                                                                            H red                                    72                                                                                 ##STR111##     "       "        H orange                                 73                                                                                 ##STR112##     "                                                                                      ##STR113##                                                                            H violet                                 74                                                                                 ##STR114##     "       "        H orange                                 75                                                                                 ##STR115##                                                                                    ##STR116##                                                                           "        H red                                    __________________________________________________________________________

EXAMPLE 76

24.2 Parts of 1-amino-2,5-dichlorobenzene-4-sulfonic acid are stirredinto 100 parts of a mixture of glacial acetic acid and propionic acid(volume ratio 17:3) and are diazotized, at 5° C., with an aqueoussolution of 7 parts of sodium nitrite. The diazotization is completeafter about 2.5 hours and the excess nitrite is destroyed with a smallamount of urea. 26.5 Parts of 4-phenyl-2-(phenylamino)-thiazole are thenintroduced, in portions. As the coupling progresses, the reactionmixture becomes viscous, and is diluted with 200 parts of glacial aceticacid. The coupling is complete after about 1 hour. The batch is dilutedwith 2,000 parts of water and briefly heated at 60° C., the product isfiltered off and washed with a small amount of water, and the filtercake is dried under reduced pressure at 60° C. The resulting monoazodye, which has the formula ##STR117## dyes nylon 6 in bluish red hueshaving good fastness characteristics.

The dyes listed in the Table which follows can be prepared similarly toExample 76.

    __________________________________________________________________________     ##STR118##                                                                   Ex-                                                                           ample                                                                             D        B        B.sup.1 B.sup.2 Hue                                     __________________________________________________________________________    77                                                                                 ##STR119##                                                                            C.sub.6 H.sub.5                                                                        C.sub.6 H.sub.5                                                                       H       orange                                  78                                                                                 ##STR120##                                                                            "        "       H       "                                       79                                                                                 ##STR121##                                                                             ##STR122##                                                                            "       H       "                                       80                                                                                 ##STR123##                                                                            "        "       H       "                                       81                                                                                 ##STR124##                                                                             ##STR125##                                                                            "       H       "                                       82                                                                                 ##STR126##                                                                            C.sub.6 H.sub.5                                                                        "       H       "                                       83                                                                                 ##STR127##                                                                            "        "       H       "                                       84                                                                                 ##STR128##                                                                            "        "       H       "                                       85                                                                                 ##STR129##                                                                            "        CH.sub.2 CHCH.sub.2                                                                   CH.sub.2 CHCH.sub.2                             __________________________________________________________________________

The following dyes may also be prepared similarly.

    __________________________________________________________________________     ##STR130##                                                                   Ex-                                                                           ample                                                                             D.sup.1           B               B.sup.1    B.sup.2                      __________________________________________________________________________    86                                                                                 ##STR131##                                                                                      ##STR132##     C.sub.2 H.sub.5                                                                          C.sub.4 H.sub.9              87  "                 "               C.sub.3 H.sub.7                                                                          C.sub.3 H.sub.7              88                                                                                 ##STR133##       "               C.sub.4 H.sub.9                                                                          C.sub.4 H.sub.9              89                                                                                 ##STR134##       "               C.sub.2 H.sub.5                                                                          C.sub.2 H.sub. 5             90                                                                                 ##STR135##       "               "          "                            91                                                                                 ##STR136##       "               CH.sub.2 CHCH.sub.2                                                                      CH.sub.2 CHCH.sub.2          92                                                                                 ##STR137##                                                                                      ##STR138##     C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5              93                                                                                 ##STR139##                                                                                      ##STR140##     C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5              94                                                                                 ##STR141##                                                                                      ##STR142##     C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5              95                                                                                 ##STR143##       "               "          "                            96                                                                                 ##STR144##       "               "          "                            97                                                                                 ##STR145##                                                                                      ##STR146##     "          "                            98                                                                                 ##STR147##       "               CH.sub.2 CHCH.sub.2                                                                      CH.sub.2 CHCH.sub.2          99                                                                                 ##STR148##                                                                                      ##STR149##     C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5              100 "                                                                                                ##STR150##     "          C.sub.4 H.sub.9              101 "                                                                                                ##STR151##     "          "                            102 "                                                                                                ##STR152##     "          "                            103                                                                                ##STR153##       C.sub.6 H.sub.5                                                                                ##STR154##                                                                              H                            104 "                 "                                                                                              ##STR155##                                                                              "                            105                                                                                ##STR156##       "                                                                                              ##STR157##                                                                              "                            106                                                                                ##STR158##       C.sub.6 H.sub.5                                                                                ##STR159##                                                                              H                            107 "                 "                                                                                              ##STR160##                                                                              "                            __________________________________________________________________________

We claim:
 1. A light fast and wet fast acid azo-dye containing athiazole coupling component and having the formula: ##STR161## wherein Dis phenyl or naphthyl substituted by arylazo, R is C₁ -C₄ -alkyl,β-carboxymethyl, or phenyl which is unsubstituted or substituted bychlorine, bromine, methyl, ethyl, C₁ -C₄ -alkoxy, β-cyanoethyl,β-carboxylethoxy, phenoxy, sulophenoxy, C₁ -C₄ -alkanoylamino,phenylamino, sulfophenylamino, sulfoethylamino, or hydroxysulfonyl andR¹ and R² independently of one another are C₁ -C₈ -alkyl, C₂ -C₈ -alkylwhich is substituted by hydroxyl, carboxyl, hydroxysulfonyl, cyano,phenyl, C₁ -C₈ -alkoxy, phenoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄-alkoxycarbonyl, C₁ -C₄ -alkanoylamino or C₁ -C₄ -alkoxycarbonyloxy,allyl, phenyl-C₁ -C₅ -alkyl or phenyl which is unsubstituted orsubstituted by chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, cyano,carbamoyl, or hydroxysulfonyl.
 2. The azo dye of claim 1, of theformula: ##STR162## where n is 0 or 1,R³ is C₁ -C₄ -alkyl and D, R¹ andR² have the meanings given in claim
 1. 3. A light fast and wet fast acidazo dye containing a thiazole coupling component and having the formula:##STR163## wherein D is phenyl or naphthyl substituted by arylazo, R isacetyl; benzoyl; C₁ -C₄ -alkyl; C₁ -C₄ alkyl substituted by chlorine,bromine, cyano, hydroxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄-alkylmercapto, phenoxy, sulfophenoxy, phenylmercapto, amino, N-mono- orN,N-di-C₁ -C₄ -alkylamino, phenylamino, sulfophenylamino, C₁ -C₄-alkanoylamino or sulfoethylamino; vinyl; cyclohexyl; phenyl; thienyl;thiazolyl; or phenyl, thienyl or thiazolyl substituted by fluorine,chlorine, bromine, hydroxyl, C₁ -C₄ -alkoxy, β-C₁ -C₄-alkanoyloxyethoxy, β-cyanoethoxy, β-carboxylethoxy, β-C₁ -C₄-alkoxycarbonylethoxy, phenoxy, sulfophenoxy, C₁ -C₄ -alkylmercapto,phenylmercapto, amino, β-C₁ -C₄ -alkanoylamino, benzolyamino, C₁ -C₄-monoalkylamino or -dialkylamino, phenylamino, sulfophenylamine, C₁ -C₄-alkylsulfonylamino, phenylsulfonylamino or hydroxysulfonyl; R¹ and R²independently are hydrogen; C₁ -C₈ -alkyl; C₁ -C₈ -alkyl interrupted byoxygen and substituted by hydroxyl, carboxyl, cyano, chlorine, bromine,phenyl, C₁ -C₈ -alkoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyl, C₁-C₄ -alkanoylamino, acetyl, C₁ -C₄ -alkylaminocarbonyloxy,arylamino-carbonyloxy, C₁ -C₄ -alkoxycarbonyloxy or phenoxycarbonyloxy;allyl; methallyl; propargyl; cyclohexyl; phenyl-C₁ -C₅ -alkyl; phenyl;naphthyl; or phenyl or naphthyl substituted by fluorine, chlorine,bromine, C₁ -C₄ -alkoxycarbonyl, carboxyl, nitro or C₁ -C₄-alkanoylamino; or R¹ and R² together with the nitrogen atom arepyrrolidino, piperidino, morpholino, piperazino, α-methylpiperazino,hexamethyleneimino or thiomorpholino-S-dioxide; and wherein the moleculecontains from 1 to 4 --SO₃ H groups in at least one of the D, R, R¹ andR² radicals.
 4. The acid azo dye of claim 2, wherein said radical R isCH₃, C₂ H₅, CH₂ Cl, CH₂ CN, CH₂ OH, CH₂ --CH₂ Cl, CH₂ --CH₂ OH, CH₂--CH₂ CN, CH₂ --COOCH₃, CH₂ COOC₂ H₅, CH₂ --COOH, CH₂ --NHC₂ H₄ SO₃ H,--CH₂ OCH₃, --CH₂ OC₂ H₅, CH₂ SCH₃, CH₂ N(CH₃)₂, C₆ H₅ OCH₂, HO₃ SC₆ H₄OCH₂, C₆ H₅, ClC₆ H₄, BrC₆ H₄, FC₆ H₄, Cl₂ C₆ H₃, CH₃ C₆ H₄, (CH₃)₂ C₆H₃, CH₃ OC₆ H₄, C₂ H₅ OC₆ H₄, NCC₂ H₄ OC₆ H₄, CH₃ OOC.C₂ H₄ OC₆ H₄,HOOC--C₂ H₄ OC₆ H₄, H₂ NCOC₂ H₄ OC₆ H₄, CH₃ COOC₂ H₄ OC₆ H₄, HOC₂ H₄ OC₆H₄, HOC₆ H₄, C₆ H₅ OC₆ H₄, HO₃ SC₆ H₄ --OC₆ H₄, CH₃ SC₆ H₄, C₆ H₅ SC₆H₄, NC--C₂ H₄ SC₆ H₄, CH₃ CONHC₆ H₄, C₂ H₅ CONHC₆ H₄, H₂ N--C₆ H₄, HOC₂H₄ NHC₆ H₄, (C₂ H₅)₂ NC₆ H₄, CH₃ SO₂ NHC₆ H₄, C₆ H₅ SO₂ NHC₆ H₄, C₆ H₅NHC₆ H₄, CH₃ CONHC₆ H₃ SO₃ H, CH₃ OC₆ H₃ SO₃ H, ##STR164##
 5. The acidazo dye of claim 2, wherein said radicals R¹ and R² are each hydrogen,methyl, ethyl, propyl, butyl, β-hydroxyethyl, β-methoxyethyl,γ-methoxypropyl, β-cyanoethyl, β-carbomethoxyethyl, β-carboethoxyethyl,β-acetoxyethyl, β-ethoxycarbonylethyl, γ-acetylaminopropyl,phenoxycarbonyloxyethyl, phenylaminocarbonyloxyethyl,butylaminocarbonyloxyethyl, benzyl, β-phenylethyl, phenyl, sulfophenyl,disulfophenyl, acetylaminophenyl, carboxyphenyl, cyanophenyl,chlorophenyl, sulfoethyl, ##STR165##